09) ntnanm^w
(43) mffi'AMB
2001 ^4 ^12 B (12.04.2001)
PCT
! niii ifoiiii i] mi n ii rn fin i d hi nm nn am dki mi limn im mi ff u
. (io) gpsfci?f]§#
WO 01/25776 Al
(5i) m&mm®'':
(21) @{Stb^S#:
(22) DBSttiElB:
(25) U®tHH0>£8§:
(26) BKtaMaffffi:
(30) Sjtftf-^:
*$JSS¥l 1/284871
GO IN 27/327, C12Q 1/00
PCT/JPOO/06853
2000^10^2 H (02.10,2000)
B*f§
1999^10 ^5 0 (05.10.1999) JP
(71) tiMX(*B*to<±X<Dl£&miZ'DlvC):&T* t
§§&gftx££tt (MATSUSHITA ELECTRIC INDUS-
TRIAL CO., LTD.) [JP/JP]; T 571-8501 *Klff nXfli
FIX I006#tfe Osaka (JP).
(72)
(75)
fc cfc 1/
*W%/fflMA f#BI::oi\Ta>#;:
(WATANABE, Motokazu) [JP/JP]; f 576-0034 * R5
IS $ if tftiH 4-28-402 Osaka (JP). &JI|£?-
(YUGAWA, Keiko) [JP/JP]; T 63 1-0041 ^gi^g
m¥©*fa&T6T@ 708-1-513 Nara (JP), ^ffl&g
(YOSHIOKA.Toshihiko) [JP/JP]; T 573-0035 *B£Jfr&
J5 rfj KSBT 1 5- 1 5-307 Osaka (JP). MX 5&#! (NANKAI,
Shiro) [JP/JP]; T573-0071 *BMJttArfr3B^f*4-5(M2
Osaka (JP). ^lUffl^ (NAKAYAMA, Junko) [JP/JP];
T 791-0221 «»*a*»*«BT**±»¥298.|
Ehimc (JP). (MIYAZAKT, Shoji) [JP/JP]; T
791-8032 a&lfctfilJj m*l£Sl£Bn052 Ehime (JP). M>
**fT (BABA, Hidcyuki) [JP/JP]; f 790-0923 SttM
t^ULl m ft &#»T340-2 Ehime (JP).
(74) ftSA: 5#f0fiI5(ISHlI, Kazuo); =P541-0041 *85fff
*Ri!T**B:lt3l2TB3«6# tt&UJ#tf;U Osaka
(JP).
(8i) fe&m (mtv- ca, cn, jp, us.
(84) ffiSUfffiity: 3 -Dy/Wft (AT, BE, CH, CY, DE,
DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE).
BttttHftH:
(54) Title: GLUCOSE SENSOR
(54) £JE0)£ft: yjua-x-fe:/-*
IT)
O
Ui VT7
(57) Abstract: A glucose sensor having an electrically insulating substrate, provided thereon, an electrode system comprising a
working electrode and a counter electrode and, formed in contact with or adjacent to the electrode system, a reacting layer comprising
glucose dehydrogenase with pyrroloqunoline as a coenzyme, wherein the reacting layer contains at least one additive selected from
the group consisting of gluconic acid and salts thereof. The glucose sensor is a high performance sensor which is excellent in storage
stability and exhibits improved response characteristics.
mm*)
WO 01/25776 Al IIIll«lllllllllOiNIIIIIlllll!Illlllllll
(57)
*fsgm, **tt5&«m±ufc, KtttBft^;i/3-
x-fc>i7-£ts&;t5. :ot>tn, «&il8iRtt£«> WIHS«±tc^
WO 01/25776
1
PCT/JP00/06853
m m - m
2 - 0 6 2 9 5 2 o
#3&«a7can*. torn, »^£ttfc*^g«#£*&fb¥WfcKi*tu
WO 01/25776
2
PCT/JPOO/06853
rPQQ-GDHj it* 5. ) ^fflmtlTl^. PQQ-GDH£ffl
V^^;|/3-X-fe>+Ki, P QQ - GDHfCfcrofflftllftJCII^
toZ-Lfc^lttbs MXRJ&ifi&L*-b £©$£K*©J&»££< gttfc'tr*
ZMfemt, Kff««f©l*»Ei:J;^Ttf6o<:i:Aiftn t T&fr
WO 01/25776
3
PCT/JP00/06853
£ Vt Z> n £ & IrI ± L £ ft tt tlft if ) V □ - X -fe > it $ ft & T § £ t £ g
§ H <!: W £ LVi.
I
WO 01/25776 PCT/JP00/06853
4
EI 5 ttgjfiffl l ©soio.-a-fe >ij-*3 «fc tXit ft ft l ©£Om~x-tr>
it © ft # W © m T & -5 „
EI 6 ft 9i©g ttffl 2©^3-^t>tOJ6:t?1#ttH7»5.
El 7 2 ©^;i/n-xiz> ; 9-^J;lXi:bfeFiI 1 ©^;ua-x-te>
iJ-©##fi&©££!ftttBT&*.
El 8 tt*58W©H*fi0!l 3 ©^□-Xiz>1f0/&g#'MT"&3.
El 9 ttgjfi^ 3 ©^;m-^-fe>u-*«t^jttt« i ©^;m-x-tz>
El 1 0 «*^H^©^S£f!|4©^;i/n--fe>1t©^^i|#ttEl-C ! fe-5o
El i i tt£««4 ©^3-x-fe>iJ-;fe«fctfttftW i ©y;m-x-b
>it © u& lij © ei r $> z .
±IB©«k3fc:, *f6^©y;m-x-fe>ittt, iiiLtPQQ-
#S2g§#SW:, P QQ - GDH££tTKJS»K, 4f;H3 >B6i$ «fc /
flf©#*fc£ ©3S*0SE{fcj&> 5 PQQ-GDH$§Il> Ztl\Z&?T
^3 >&45<fctf/£fc'tt^©ft£ PQQ-GDH©^£fe«£KjSg
WO 01/25776
5
PCT/JPOO/06853
b P QQ- GDH**3&Kfii«T* - tifi-VZZ. BB^fe
■
m;wk >$?$3&£#&tf ens. #k:, ^^n>i^u^A^
v^;m-x-tz z ttfu-zz* z\z\-c\ y ? > z mtte. m
7)ln>m%>£tf^(Di&\ZteR&U^tf, P QQ-GDHJ^It
^l:, 7$)Vm, Tl/-f>^, □ *J;?>'^nb©^tt7Ktc^
WO 01/25776
6
PCT/JP00/06853
^Ct'Oi^NaOH, K0H3tt£O7;P* ijcj; 0 3f*OpHk:HBt
TS««»ri5tt*k:*3inT*itf«ki». «F3i*pHtt. 5. o~8. 5 r
■ »Il;^tV»fl!i&«T»40T, mi t> o T # * £ 8s in T 5 «fc 0 , i^lo
fesmfcgsiJDl-^Tf&a. zti Z <Dmt\MZ$ ts >? )\/ n - x~k > Vlt ,
.tm«£ LTM.O . 5 ~ 5 # 1 SiiMtitSi^iT^-fyfl)
-.■fe>-U"7?tt, ®i!0. 2-2 0U/t>f C^LT, ±1B^;H3>K
ssfctt-to&ossjbnatt, i. 5 ~ i 5 o n g/t >u-©i6B*e*ntt
«t<. ®&£fe&t7y>?m<Z)i&mikt ^SfL»<=>, 15-50
&£t^ti£©ig©jijraste, Bdia-fe i/T, o. 025
tHT^CWilk Utta-y'h (uni t) £3tT.
-m\Z, A;i/y^A<t>li, PQQ-GDH^'-ift
^JtictsiLO. mttui'isv A<Dmmm\z. ±§a©-tz>-y-t;:#LT, 5
WO 01/25776 PCT/JPOO/06853
7
H D^->x^;Hr;i/n-x, t HD + y^n fcf ;Hz ;u p — 7. , ^^;Hr
;i/#^->x^;nr;i/p-x, # u t*->tf p u h >, #y brxjP7';m
WO 01/25776
8
PCT/JP00/06853
S*&i4fcJg«£4;ifc^fc ©■?&£©;&<#£ L < , fll&tf £>>ifiLill7
;U7S> ( B S A ) , 5P7^y5>, JlitfT*
*yu-7s, x^p-x, ^^h-x, t;h--x, M/ad-x,
^h'j>, 75P-7, -f*u>,
□ 1*3 >, Oi/h-JK v>-h-;u, y;nfh-;p, UHh-j^
J; tfx** > 3 £ * & Vf 2> Z t **T # 5 .
WO 01/2577fi
9
PCT/JPOO/06853
□ - ; v m s ct & t * * > n - ; p m. & a # & \i e. n 5 .
#BffJ£ttiffl£ ITU *>tt© I, .
-t-Offi. Jh^K. £fc*U*A, ^{fci-h.'J^A, fiEB&7>
^E-^A, yiJ-feP-JU, 7^H-;P, EDTA, EGTA, DTT,
dte, gsh, 2 7 ; -frfcZzmtoVThk^.
zn*> <D%%.{tmz>m\\m\z. pqq-gdhoio 0 a*«K:#L
T, 0. 0 1-1 0 OfiS&T&SJIttffiF^LH.
tfD U*cJ U >*/ > (PQQ) PQQ-GDH*
PQ'QO^JPfitt, 0. O4~2Ong/t>tTS50^IilH.
#S6ETffl^S»sliPQQ-GDH«:. >>1"n©iBB© t> 0 feffl H S
PQQ-GDH$ffl^fc^3-7t>1j-|t £ffi(I>
KT.C, **W*ffl^T*?BW*R5a-r53J«. *589J tt H tl 6 CD * £
■ B 1 fit. *%W<D~*MM£l3ttZrt4*±>y<DRf&M*ftQm*
U- H 2 t»»UT^5. $6(3, lOlSlill, *felitt^-7sh£
EPS'J LTlglil 6 &JBJ5fcLTV>3. Ife^S 6 te, f£ffl® 4 ©ftjIJg&£M
WO 01/25776 PCT/JP00/06853
10
1 05tt5X^-t 8 &J;tf£MTL 1 1 £{fx.fc# /t- 9^110-
3 ftfilli^ o.tgttS . i I: J; D , /W ^-fe >
0 2 *^0j^ck§;w ;f -t > if 3 „ sm^eS
^Tfc«kV>. RjSS7tt, 0^O^JT*«, ib.KftJSft'^ JI 7 a ^©
;i/n-xot h u # a& (&r> rcMcj tmr* ) 00. 5wt%
*»I*5# l»Tl<, 5 0TC©fi««»»'tf»"C 1 0»Mftjl»$«,
CMCI7 a^f^lfc. 1 0 0 OU/ml OPQQ-GDH,
7 ±\Z 5 At l»Tl, Sil.T« 17b ZMf&Ltzo Z.<D£o\ZLTif
o^H, lisMi L/T> ^;io-Xiia?j&*3 0~6 2 Omg/d 1 i
fc*J:3fc*»l,fcjli*fcffl*Ufc. fit, £cz>it&iK£EjfcS 7 ±
<Dif)Vn-7,UP QQ - GDHickOSfb^ns. ^IT, :ftiHR
WO 01/25776
11
PCT/JPOO/068S3
££f&!4'©7 x 'J y7 >ffc# U £ A** 7 x □ ->7 >itfi U 9 A JcStc.
$ns. k»***tut^6 3 o^^ic, ttmszmmizv
Tftmm4\Z+ 0 . 5 V©mi££MLT, 7 x □ v 7 Wt * U "7 A *
WtfcLtc. fit, 5S>«t^ffitt^fflSOK*«ltn5*SSIIS:ill!lSL
o^W3-^»*K:iii»*nfcjiittte*ti/T«ij(E«ftiiijgL, a
T. ,4 Ott 1 »W«#»©*>tf®j&«tt#ftTLT^a
1
tt&fll 1 t W\m\Z LTCMC J| 7 a £^fi£Lfc^, 1 000 U/m 1
OPQQ-GDH, 5 0 mM © 7 x U v 7 >4b# U 7 A£ <fc IS 4 OmM
©^;Hi>i!* >J £ A trig CMCl7ail;5/z IS
®m®$$fo-c4 octi jSp B m#tfc^©-fe>+nc^^Tjts##ttgi$
WO 01/25776
12
PCT/JPOO/06853
4 0 0 mg/d 1 ^±0fg«fc*JWSJ6§«aiffi©<ST^/h$ <&?T
U£AS£*fctr»2f;io-;*-fe>lj-«k 0, 6 0 0 mg/d 1 #j£
il^J 2
Jti&#iJ 1 i^Hit UTCMCil ZaSjfElUci, 1 0 0 0 U/m 1
CDPQQ — GDH, 5 0mM©7i l Jy7>fWJ')A 1 40mM<D7*
>B6# U 2A:fe«fctf 0 . 5mM0 7*;i'&7Ka§:& <J <7AS#tfzl-a-
CMCl7ait5tf liTLSiH, l7b€IfiElfc,
f£j&Lfc. f(D^I^i6 1;if 5 06J;t), fP«iaao-fe>1J-t 4 0
^^©jt^sui 7 tc^r. E7§i5i, u 9A££tf
WO 01/25776 PCT/JPOO/06853
13
fflMJ 3
•Jfcttfll lt^8HcLTCMCl7a£^)&L£t£>100 OU/ra l
OPQQ-GDH, 5 0mMO7xiJ-/7>liJ'J^A, 40mMtf>^
CMC® 7 ail:5(i l i»T Uft<, g7b£^J&Ufc. Z<D£o
ct i »iia##&©^>i*©£§#ftK:m3:iAy£3mft< , ifct&fli i
>+M*, 6 0 0 mg/d 1 ttifi0J6Sfflj&«ftV». CI
ft ft « £ & 1 1 -a ^ ; 1/ □ - x -fe > -y- © j& g 14 € & * r * 5 c <h a* to ^ * .
Jt^^Jltl^^fCtTCMC®7 a £7fmt£:&> 1 0 0 0 U/m. 1
I
WO 01/25776 PCT/JPOO/06853
1 4
WPQQ-GDH, 5 0mMO7x'Jx7>ft*'J l )A, 40mMO^
JHl>^# U 0 A&cktf 0 . 5 mMffl IS ££tl
CMCi7alC5(i 1 SSTLSigLT, l7b^)f^Lt„ Z.<D&?
f£j£Lfc. ^©^H£SI 1 0 l:^T. mi 0 'J; D , ftmW.'&<D± >V £
MJ©ir>1f ©&#M©jfcg#14©tfct££0 1 1 CSt. El 1 UI5
6 0 0 mg/d 1 ttiEfcW-SfcflFMtffcV*. dti»c«fcO, >®?#
ir>tf0««tt*3fcST?# -set
^SS^J 5
ttlSMl tmm\Z LTCMCI 7 a £^J&Lfc&, 1 000U/ml
©PQQ-GDH, 5 0 mM©7 x U ->7 >fL# U £ A, 40mM©^
^□>K*U^A, 0. 5mM©7*^B&**;fr U A*J;t*7 5 tf M
©*<fc:fr;U*> CMC17 a±C5a 1 iTl
Silt, l7bSMLfc. c ©i 3 £ LT^;U3-Xiz >it
Lfc,
WO 01/25776
15
PCT/JPOO/06853
4 5 i isp^#m©-fe >it©^g#ttK«ff£ a,<»:M«& < , 4 5
WO 01/25776
16
PCT/JPOO/06853
Iff # CO 15 ffl
© ^ S P JW £ "a" tr ^ ; 1/ □ - x ± > +)- o
2. MISERS**, SSfc, 7^;i/^,. '7^^lCt, "7
t i a oifcjnjffl his i mizmm<D!f)in-z
5. WBKJSJI**, £ 6 ICttT- ;*x w X— * Sr^tfW *£>i5ffl|g l ~ 4
WO 01/25776
2/7
PCT/JP00/06853
WO 01/25776
3/7
PCT/JP00/06853
WO 01/25776
4/7
PCT/JP00/06853
WO 01/25776
5/7
PCT/JP00/06853
FIG.7
0 100 200 300 400 500 600 700
£OUa— XMCmgAil)
FIG.8
0 ' 1 1 1 : — I
0 100 200 300 400 500 600 700
£*;Uzi-X;!]*(mg/dl)
WO 01/25776
6/7
PCT/JPOO/06853
FIG.9
12
10
1 8
m
.6
A 4
2
0
I
J
100 200 300 400 500 600 700
?>:=]-X;SJt(mg/dl)
FIG.10
12
10
1 8
^ 6
2
0
\
1
Hh — —
100 200 300 400 500 600 700
•7;U3-X;!J*(mg/dl)
WO 01/25776
7/7
PCT/JPOO/06853
FIG.11
12
10
1 8
£ 6
A 4
2
0
~* a j*— /mi /
— i-
j
7
-7"
0 100 200 300 400 500 600 700
y;U=l-X;Ilt(mg/dl)
ill i H/lvliAl LKJiy AL orl AKl_rl ivllfr UK1
PCT/JP00/06853
A. CLASSIFICATION OF SUBJECT MATTER
Int. CI 7 G01N27/327 C12Q1/00
According to International Patent Classification (IPC) or to both national classification and IPC
B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
Int. CI 7 G01N27/327 C12Q1/00
Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched
Jitsuyo Shinan Koho 1922-1996 Toroku Jitsuyo Shinan Koho 1994-2000
Kokai Jitsuyo Shinan Koho 1971-2000 Jitsuyo Shinan Toroku Koho 1996-2000
Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)
JOIS: GLUCONIC ACID* PYRROLOQUINOLINE (in Japanese)
CA(STN) : [PYRROLOQUINOLINE (W) QUINON] * [GLUCONIC (W) ACID?] * ELECTRODE?
C. DOCUMENTS CONSIDERED TO BE RELEVANT
Category*
Citation of document, with indication, where appropriate, of the relevant passages
Relevant to claim No.
JP, 10-227755, A (Matsushita Electric Ind.
25 August, 1998 (25.08.98),
Claims 1 to 5 (Family: none)
Co. , Ltd. ) ,
1-5
I I Further documents are listed in the continuation of Box C. Q See patent family annex.
* Special categories of cited documents:
"A" document defining the general state of the art which is not
considered to be of particular relevance
M E" earlier document but published on or after the international filing
date
M L M document which may throw doubts on priority claim(s) or which is
cited to establish the publication date of another citation or other
special reason (as specified)
"O" document referring to an oral disclosure, use, exhibition or other
means
"P" document published prior to the international filing date but later
than the priority date claimed
"T" later document published after the international filing date or
priority date and not in conflict with the application but cited to
understand the principle or theory underlying the invention
"X" document of particular relevance; the claimed invention cannot be
considered novel or cannot be considered to involve an inventive
step when the document is taken alone
u y document of particular relevance; the claimed invention cannot be
considered to involve an inventive step when the document is
combined with one or more other such documents, such
combination being obvious to a person skilled in the art
"& M document member of the same patent family
Date of the actual completion of the international search
12 October, 2000 (12.10.00)
Date of mailing of the international search report
24 October, 2000 (24.10.00)
Name and mailing address of the ISA/
Japanese Patent Office
Facsimile No.
Authorized officer
Telephone No.
Form PCMSA/210 (second sheet) (July 1992)
BS1S3S&&
bbub#? pct/jpoo/o6 853
a. &m<o&-rz#w<oftm mm®?&m (ipo )
Int. CI. 7 G01N27/327 CI2Q1/00
B.
Int.C1.7 G01N27/327 CUQ1/00
H#BfU8§r3e4i« 1922-199 6?
B^m^nmmm^m 1971-2000?
B*BS®HfflST&&$a 1994-2000?
B*SXffl*r$9ft&tt 1996-2000?
JOIS : r*3Vfy*fp»^J^5/
a(STN):[PYRROLOQUIN0LINE (W) QUINON] * [GLUCONIC (W) ACID?] * ELECTRODE?
JP. 10-227755, A (&TU£$tt££4±) 25. 8^ . 1998 (25. 08. 98)
1-5
□ cBotttfcfciJfcWMteivcv**.
muffin b
Taj #K:Haro*>5XiRT?l±<c'<
BBUBBtt0ttB*fcttm i F-c*>&#
TEj
roj
rpj
-BttfiMfoicBfcii*?- l"Tj BBaBBXtt«*B«fc^3*tfcSBtt*>oT
12. 10. 00
BK«HEff£«>%£B
24.10.00
BBBSEBB©*8*0*-C5te
0#(S#IT/T (1SA/JP)
3GE#-^ 100-8915
maffiTft H ESz55g§HT B 4 g 3 -
WW/?*** (BROfcSBA)
BF
2 J
8 5 0 2
USS^- 03-3581-1101
3 2 5 2
iSPCT/ISA/2 10 (12^) (1 9 9 8?7£)
THIS PAGE BLANK (USPTO)